CN109295716A - A kind of preparation method of magnetic, temperature collaboration stimuli responsive hydrogel - Google Patents
A kind of preparation method of magnetic, temperature collaboration stimuli responsive hydrogel Download PDFInfo
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Abstract
The present invention relates to the preparation methods of a kind of magnetic, temperature collaboration stimuli responsive hydrogel, include the following steps, prepare Fe by coprecipitation method first3O4Magnetic nanoparticle, by Fe3O4Magnetic nanoparticle is added in PU solution, prepares PU/Fe by Thermal inactive method3O4Magnetic composite nano fiber.N-isopropyl acrylamide is grafted on PU tunica fibrosa finally by ultraviolet radioactive graft polymerization procedure.Using the bigger serface and high porosity of PU nanofiber, hydrogel is made to be conducive to the diffusion of hydrone in swelling and contraction, substantially increases the speed of response of hydrogel.Utilize the Thermo-sensitive of n-isopropyl acrylamide, Fe3O4Magnetism, make preparation PU-g-PNIPAm/Fe3O4Composite nano fiber hydrogel has magnetic, temperature dual responsiveness.
Description
Technical field
The present invention relates to the preparation methods of a kind of magnetic, temperature collaboration stimuli responsive hydrogel, belong to macromolecule hydrogel technology
Field.
Background technique
Hydrogel is appropriately crosslinked and has three-dimensional space network structure, can be swollen in water but undissolved polymer is solidifying
Glue.The volume and correlated performance variation that response can be generated to environmental stimuli, can be swollen rapidly, water suction reaches full in water
With.Environmental response intelligent aqueous gel many fields have important application value, response environmental information (such as pH, temperature, light,
Electric field, magnetic field etc.) minor change, generate corresponding volume change or the variation of other physicochemical properties.Responsiveness intelligence
Energy hydrogel common problem is that stimuli responsive is relatively simple, the speed of response is slow.Compared with single stimuli responsive hydrogel,
Multiple response hydrogel can integrate the advantages of single response hydrogel simultaneously, embody in terms of constructing intelligent response material very big
Advantage.Multiple response hydrogel is more to be shown: pH and temperature double-bang firecracker answer, temperature and magnetic field double-bang firecracker are answered, pH and light double-bang firecracker are answered,
PH and ionic strength double-bang firecracker are answered, light and heat double-bang firecracker is answered etc..How multiple response intelligent aqueous gel is constructed as people's research
Hot spot.
Summary of the invention
The object of the present invention is to provide the preparation methods of a kind of magnetic, temperature collaboration stimuli responsive hydrogel.
The present invention is achieved by the following technical solutions:
The present invention provides the preparation methods of a kind of magnetic, temperature collaboration stimuli responsive hydrogel comprising following steps:
Frerrous chloride and iron chloride are dissolved in distilled water, ammonium hydroxide is added, after reaction, obtains magnetic ferroferric oxide nanometer
Particle；
Polyurethane is dissolved in N, N '-dimethyl formamide/tetrahydrofuran in the mixed solvent, after dissolving completely described in addition
Magnetic ferroferric oxide nanometer particle, obtains quenching liquid；
After the quenching liquid is quenched at -40~-10 DEG C, N, N '-dimethyl formamide/tetra- are removed with distilled water
Hydrogen furans mixed solvent, freeze-drying obtain polyurethane/Fe 3 O 4 magnetic composite nano fiber；
By the n-isopropyl acrylamide, N, N '-methylene-bisacrylamide and ammonium persulfate are dissolved in distilled water, add
Enter modified manometer silicon dioxide, after being uniformly dispersed, the polyurethane/Fe 3 O 4 magnetic being added by benzophenone activation is compound
Nanofiber is reacted with ultraviolet light irradiation under nitrogen protection, obtains polyurethane grafted poly-N-isopropyl acrylamide/tetra- oxygen
Change three-iron magnetic composite nano fiber hydrogel, i.e., the described magnetic, temperature collaboration stimuli responsive hydrogel.
Preferably, the molar ratio of the frerrous chloride and iron chloride is 1:2, and the concentration of ammonium hydroxide is 1mol/L,
Cool time is 1~3h.
Preferably, the polyurethane, N, N '-dimethyl formamide, tetrahydrofuran and magnetic ferroferric oxide are received
The mass ratio of rice grain is 1:(8~16): (2~6): (0.05~0.1).
Preferably, the modified manometer silicon dioxide the preparation method comprises the following steps:
Vinyltriethoxysilane is dissolved in ethyl alcohol, silica is added, is uniformly dispersed, after being ultrasonically treated 2h,
Centrifuge separation, ethanol washing are dried in vacuo at 50 DEG C, obtain modified manometer silicon dioxide.
Preferably, the vinyltriethoxysilane, ethyl alcohol, silica mass ratio be 1:25:1.
Preferably, the polyurethane/Fe 3 O 4 magnetic composite nano fiber activation method are as follows:
Polyurethane/Fe 3 O 4 magnetic composite nano fiber is soaked in the acetone soln of benzophenone, after 5min
It takes out, vacuum drying is spare.
Preferably, the quality of the polyurethane/Fe 3 O 4 magnetic composite nano fiber, benzophenone, acetone
Than for 1:5:95.
Preferably, the n-isopropyl acrylamide, N, N '-methylene-bisacrylamide, ammonium persulfate and change
Property silica mass ratio be 100:4:(1~2): (2~4).
Preferably, the n-isopropyl acrylamide and polyurethane/ferroferric oxide magnetic nano after activation
The mass ratio of composite fibre is 10:(1~1.5).
Mechanism of the invention is:
Fe is prepared by coprecipitation method3O4Magnetic nanoparticle, by Fe3O4Magnetic nanoparticle is added in PU solution, leads to
Cross thermotropic phase disengagement method preparation PU/Fe3O4Magnetic composite nano fiber, the diameter of fiber about 500nm.Finally by ultraviolet spoke
It penetrates polymerization n-isopropyl acrylamide is grafted on PU tunica fibrosa.Bigger serface and high hole using PU nanofiber
Gap rate makes hydrogel be conducive to the diffusion of hydrone in swelling and contraction, substantially increases the speed of response of hydrogel.It utilizes
Thermo-sensitive, the Fe of n-isopropyl acrylamide3O4Magnetism, make preparation PU-g-PNIPAm/Fe3O4Composite nano fiber water-setting
Glue has magnetic, warm dual responsiveness.
Benzophenone activates PU/Fe3O4The purpose of magnetic composite nano fiber is that PU is made to form free radical, is conducive to subsequent purple
External radiation graft polymerization reaction.Modified manometer silicon dioxide is added in reaction system, makes the discrete network hole of gel-forming
Structure, porosity improve, and temperature-responsive rate greatly improves.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, PU/Fe is prepared by Thermal inactive method3O4Magnetic composite nano fiber, simple process, yield are high, very
It is suitable for industrialized production；
2, n-isopropyl acrylamide is grafted to the PU nanofiber film surface with biocompatibility, reduces gel
Volume size, increase specific surface area and porosity, temperature-responsive rate greatly improves；
3, will have magnetic Fe3O4Nano particle is added in aquogel system, and the hydrogel of preparation is made not only to have temperature
Responsiveness is spent, also there is magnetism.
4, the addition of modified manometer silicon dioxide forms discrete network pore structure, and porosity improves, temperature-responsive
Rate greatly improves.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
The magnetic of the preparation of embodiment 1, temperature cooperate with stimuli responsive hydrogel scanning electron microscope (SEM) photograph in Fig. 1 present invention；
The magnetic of the preparation of embodiment 1, temperature collaboration stimuli responsive swelling behavior are than variation with temperature song in Fig. 2 present invention
Line；
Embodiment 1 prepares magnetic, temperature collaboration stimuli responsive hydrogel deswelling dynamics curve in Fig. 3 present invention；
Embodiment 1 prepares magnetic, temperature collaboration stimuli responsive hydrogel magnetization curve in Fig. 4 present invention.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
1)PU/Fe3O4The preparation of magnetic composite nano fiber
By 0.1987g FeCl2·4H2O and 0.5404g FeCl3·6H2O is added in 25g distilled water, 25 DEG C of magnetic agitations
Dissolution, it is rear that 1mol/L ammonium hydroxide 8mL, 25 DEG C of reaction 3h are added, after reaction, filters, washs, is dry, obtaining Fe3O4Nanometer
Grain, particle diameter are less than 10nm.10g DMF and 5g THF in the mixed solvent is added in 1g PU, 60 DEG C of magnetic agitation 2h make it
It is completely dissolved, by 0.05g Fe after dissolution completely3O4Nano particle is added in above-mentioned solution, high speed magnetic stirring, and it is mixed to form quenching
Close liquid.Quenching mixed liquor is quenched into 2h in -40 DEG C of refrigerators, after, distilled water is added into system, removes DMF and THF,
Every 6h changes primary distilled water, changes 4 times, finally freeze-drying obtains PU/Fe3O4Magnetic composite nano fiber.
2)PU-g-PNIPAm/Fe3O4The preparation of composite nano fiber hydrogel
1g vinyltriethoxysilane is dissolved in 25g ethyl alcohol, 1g SiO is added2, after ultrasonic disperse, ultrasonic treatment
2h, centrifuge separation, ethanol washing, 50 DEG C of vacuum drying obtain modified Nano SiO2。
Take 1g PU/Fe3O4Magnetic composite nano fiber is immersed in 5g benzophenone and 95g acetone soln, after activating 5min
It takes out, vacuum drying is spare.
By 100mg n-isopropyl acrylamide (NIPAm), 4mg N, N '-methylene-bisacrylamide (BIS) and 1mg mistake
Ammonium sulfate (APS) is dissolved in 25mL distilled water, and 2mg modified Nano SiO is added2.10mg is activated into PU/Fe3O4Magnetic composite nano
Fiber is immersed in above-mentioned mixed liquor, and N is led in system2Protection.It opens ultraviolet source (500W high-pressure sodium lamp), radiation length
50cm, radioreaction 30min.After reaction, products therefrom is washed with distilled water, is dried in vacuo, obtain PU-g-
PNIPAm/Fe3O4Composite nano fiber hydrogel, i.e. magnetic, temperature cooperate with stimuli responsive hydrogel.
PU-g-PNIPAm/Fe3O4Fibre diameter is 450 ± 210nm in composite nano fiber hydrogel, as shown in Figure 1.Hole
Gap rate and specific surface area are respectively 92.1% and 14.61m2/g。PU-g-PNIPAm/Fe3O4Composite nano fiber hydrogel reaches
Swelling ratio when swelling equilibrium is 23.27g/g.Fig. 2 is PU-g-PNIPAm/Fe3O4Composite nano fiber swelling behavior ratio with
Temperature variation curve, it can be seen that hydrogel good temperature sensitive properties nearby occurs at 32 DEG C.Fig. 3 is PU-g-
PNIPAm/Fe3O4Composite nano fiber hydrogel deswelling dynamics curve, hydrogel go water rate to reach in 1min
55.8%.Fig. 4 is PU-g-PNIPAm/Fe3O4The magnetization curve of composite nano fiber hydrogel, from the visible no magnetic hysteresis of magnetization curve
Phenomenon, remanent magnetism and coercivity are all zero, illustrate PU-g-PNIPAm/Fe3O4It is special that superparamagnetism is presented in composite nano fiber hydrogel
Sign, apparent saturation magnetization are 0.056emu/g.
Embodiment 2
1)PU/Fe3O4The preparation of magnetic composite nano fiber
By 0.1987g FeCl2·4H2O and 0.5404g FeCl3·6H2O is added in 25g distilled water, 25 DEG C of magnetic agitations
Dissolution, it is rear that 1mol/L ammonium hydroxide 8mL, 25 DEG C of reaction 4h are added, after reaction, filters, washs, is dry, obtaining Fe3O4Nanometer
Grain, particle diameter are less than 10nm.12g DMF and 4g THF in the mixed solvent is added in 1g PU, 60 DEG C of magnetic agitation 2h make it
It is completely dissolved, by 0.05g Fe after dissolution completely3O4Nano particle is added in above-mentioned solution, high speed magnetic stirring, and it is mixed to form quenching
Close liquid.Quenching mixed liquor is quenched into 2h in -30 DEG C of refrigerators, after, distilled water is added into system, removes DMF and THF,
Every 6h changes primary distilled water, changes 4 times, finally freeze-drying obtains PU/Fe3O4Magnetic composite nano fiber.
2)PU-g-PNIPAm/Fe3O4The preparation of composite nano fiber hydrogel
1g vinyltriethoxysilane is dissolved in 25g ethyl alcohol, 1g SiO is added2, after ultrasonic disperse, ultrasonic treatment
2h, centrifuge separation, ethanol washing, 50 DEG C of vacuum drying obtain modified Nano SiO2。
Take 1g PU/Fe3O4Magnetic composite nano fiber is immersed in 5g benzophenone and 95g acetone soln, after activating 5min
It takes out, vacuum drying is spare.
100mg NIPAm, 4mg BIS and 1mg APS are dissolved in 25mL distilled water, 2mg modified Nano SiO is added2.It will
10mg activates PU/Fe3O4Magnetic composite nano fiber is immersed in above-mentioned mixed liquor, and N is led in system2Protection.Open ultraviolet source
(500W high-pressure sodium lamp), radiation length 50cm, radioreaction 30min.After reaction, products therefrom is washed with distilled water,
Vacuum drying, obtains PU-g-PNIPAm/Fe3O4Composite nano fiber hydrogel, i.e. magnetic, temperature cooperate with stimuli responsive hydrogel.
PU-g-PNIPAm/Fe3O4Fibre diameter is 398 ± 210nm in composite nano fiber hydrogel.Porosity and Bi Biao
Area is respectively 90.1% and 13.99m2/g。PU-g-PNIPAm/Fe3O4When composite nano fiber hydrogel reaches swelling equilibrium
Swelling ratio be 23.40g/g.PU-g-PNIPAm/Fe3O4Composite nano fiber hydrogel goes water rate to reach in 1min
54.6%.PU-g-PNIPAm/Fe3O4The apparent saturation magnetization of composite nano fiber hydrogel is 0.053emu/g.
Embodiment 3
1)PU/Fe3O4The preparation of magnetic composite nano fiber
By 0.1987g FeCl2·4H2O and 0.5404g FeCl3·6H2O is added in 25g distilled water, 25 DEG C of magnetic agitations
Dissolution, it is rear that 1mol/L ammonium hydroxide 8mL, 25 DEG C of reaction 5h are added, after reaction, filters, washs, is dry, obtaining Fe3O4Nanometer
Grain, particle diameter are less than 10nm.14g DMF and 3g THF in the mixed solvent is added in 1g PU, 60 DEG C of magnetic agitation 2h make it
It is completely dissolved, by 0.08g Fe after dissolution completely3O4Nano particle is added in above-mentioned solution, high speed magnetic stirring, and it is mixed to form quenching
Close liquid.Quenching mixed liquor is quenched into 2.5h in -30 DEG C of refrigerators, after, be added distilled water into system, remove DMF and
THF, every 6h change primary distilled water, change 4 times, finally freeze-drying obtains PU/Fe3O4Magnetic composite nano fiber.
2)PU-g-PNIPAm/Fe3O4The preparation of composite nano fiber hydrogel
1g vinyltriethoxysilane is dissolved in 25g ethyl alcohol, 1g SiO is added2, after ultrasonic disperse, ultrasonic treatment
2h, centrifuge separation, ethanol washing, 50 DEG C of vacuum drying obtain modified Nano SiO2。
Take 1g PU/Fe3O4Magnetic composite nano fiber is immersed in 5g benzophenone and 95g acetone soln, after activating 5min
It takes out, vacuum drying is spare.
100mg NIPAm, 4mg BIS and 1.5mg APS are dissolved in 25mL distilled water, 3mg modified Nano SiO is added2。
12mg is activated into PU/Fe3O4Magnetic composite nano fiber is immersed in above-mentioned mixed liquor, and N is led in system2Protection.Open ultraviolet light
Source (500W high-pressure sodium lamp), radiation length 50cm, radioreaction 30min.After reaction, by products therefrom distillation washing
It washs, be dried in vacuo, obtain PU-g-PNIPAm/Fe3O4Composite nano fiber hydrogel, i.e. magnetic, temperature cooperate with stimuli responsive water-setting
Glue.
PU-g-PNIPAm/Fe3O4Fibre diameter is 460 ± 228nm in composite nano fiber hydrogel.Porosity and Bi Biao
Area is respectively 89.1% and 17.42m2/g。PU-g-PNIPAm/Fe3O4When composite nano fiber hydrogel reaches swelling equilibrium
Swelling ratio be 25.8g/g.PU-g-PNIPAm/Fe3O4Composite nano fiber hydrogel goes water rate to reach in 1min
52.5%.PU-g-PNIPAm/Fe3O4The apparent saturation magnetization of composite nano fiber hydrogel is 0.063emu/g.
Embodiment 4
1)PU/Fe3O4The preparation of magnetic composite nano fiber
By 0.1987g FeCl2·4H2O and 0.5404g FeCl3·6H2O is added in 25g distilled water, 25 DEG C of magnetic agitations
Dissolution, it is rear that 1mol/L ammonium hydroxide 8mL, 25 DEG C of reaction 3h are added, after reaction, filters, washs, is dry, obtaining Fe3O4Nanometer
Grain, particle diameter are less than 10nm.16g DMF and 3g THF in the mixed solvent is added in 1g PU, 60 DEG C of magnetic agitation 2h make it
It is completely dissolved, by 0.1g Fe after dissolution completely3O4Nano particle is added in above-mentioned solution, high speed magnetic stirring, and it is mixed to form quenching
Close liquid.Quenching mixed liquor is quenched into 3h in -20 DEG C of refrigerators, after, distilled water is added into system, removes DMF and THF,
Every 6h changes primary distilled water, changes 4 times, finally freeze-drying obtains PU/Fe3O4Magnetic composite nano fiber.
2)PU-g-PNIPAm/Fe3O4The preparation of composite nano fiber hydrogel
1g vinyltriethoxysilane is dissolved in 25g ethyl alcohol, 1g SiO is added2, after ultrasonic disperse, ultrasonic treatment
2h, centrifuge separation, ethanol washing, 50 DEG C of vacuum drying obtain modified Nano SiO2。
Take 1g PU/Fe3O4Magnetic composite nano fiber is immersed in 5g benzophenone and 95g acetone soln, after activating 5min
It takes out, vacuum drying is spare.
100mg NIPAm, 4mg BIS and 1.5mg APS are dissolved in 25mL distilled water, 3mg modified Nano SiO is added2。
12mg is activated into PU/Fe3O4Magnetic composite nano fiber is immersed in above-mentioned mixed liquor, and N is led in system2Protection.Open ultraviolet light
Source (500W high-pressure sodium lamp), radiation length 50cm, radioreaction 30min.After reaction, by products therefrom distillation washing
It washs, be dried in vacuo, obtain PU-g-PNIPAm/Fe3O4Composite nano fiber hydrogel, i.e. magnetic, temperature cooperate with stimuli responsive water-setting
Glue.
PU-g-PNIPAm/Fe3O4Fibre diameter is 458 ± 211nm in composite nano fiber hydrogel.Porosity and Bi Biao
Area is respectively 90.8% and 15.34m2/g。PU-g-PNIPAm/Fe3O4When composite nano fiber hydrogel reaches swelling equilibrium
Swelling ratio be 22.9g/g.PU-g-PNIPAm/Fe3O4Composite nano fiber hydrogel goes water rate to reach in 1min
55.9%.PU-g-PNIPAm/Fe3O4The apparent saturation magnetization of composite nano fiber hydrogel is 0.065emu/g.
Embodiment 5
1)PU/Fe3O4The preparation of magnetic composite nano fiber
By 0.1987g FeCl2·4H2O and 0.5404g FeCl3·6H2O is added in 25g distilled water, 25 DEG C of magnetic agitations
Dissolution, it is rear that 1mol/L ammonium hydroxide 8mL, 25 DEG C of reaction 4h are added, after reaction, filters, washs, is dry, obtaining Fe3O4Nanometer
Grain, particle diameter are less than 10nm.16g DMF and 2g THF in the mixed solvent is added in 1g PU, 60 DEG C of magnetic agitation 2h make it
It is completely dissolved, by 0.1g Fe after dissolution completely3O4Nano particle is added in above-mentioned solution, high speed magnetic stirring, and it is mixed to form quenching
Close liquid.Quenching mixed liquor is quenched into 3h in -15 DEG C of refrigerators, after, distilled water is added into system, removes DMF and THF,
Every 6h changes primary distilled water, changes 4 times, finally freeze-drying obtains PU/Fe3O4Magnetic composite nano fiber.
2)PU-g-PNIPAm/Fe3O4The preparation of composite nano fiber hydrogel
1g vinyltriethoxysilane is dissolved in 25g ethyl alcohol, 1g SiO is added2, after ultrasonic disperse, ultrasonic treatment
2h, centrifuge separation, ethanol washing, 50 DEG C of vacuum drying obtain modified Nano SiO2。
Take 1g PU/Fe3O4Magnetic composite nano fiber is immersed in 5g benzophenone and 95g acetone soln, after activating 5min
It takes out, vacuum drying is spare.
100mg NIPAm, 4mg BIS and 2mg APS are dissolved in 25mL distilled water, 4mg modified Nano SiO is added2.It will
15mg activates PU/Fe3O4Magnetic composite nano fiber is immersed in above-mentioned mixed liquor, and N is led in system2Protection.Open ultraviolet source
(500W high-pressure sodium lamp), radiation length 50cm, radioreaction 30min.After reaction, products therefrom is washed with distilled water,
Vacuum drying, obtains PU-g-PNIPAm/Fe3O4Composite nano fiber hydrogel, i.e. magnetic, temperature cooperate with stimuli responsive hydrogel.
PU-g-PNIPAm/Fe3O4Fibre diameter is 460 ± 223nm in composite nano fiber hydrogel.Porosity and Bi Biao
Area is respectively 93.1% and 14.29m2/g。PU-g-PNIPAm/Fe3O4When composite nano fiber hydrogel reaches swelling equilibrium
Swelling ratio be 26.8g/g.PU-g-PNIPAm/Fe3O4Composite nano fiber hydrogel goes water rate to reach in 1min
58.1%.PU-g-PNIPAm/Fe3O4The apparent saturation magnetization of composite nano fiber hydrogel is 0.065emu/g.
Comparative example 1
Difference from Example 1 is, in comparative example 1, step 1) Fe3O4The additional amount of nano particle is 0, final
To PU-g-PNIPAm nanofiber hydrogels, fibre diameter is 350 ± 150nm in hydrogel.Porosity and specific surface area difference
For 94.1% and 16.4m2/g.Swelling ratio when PU-g-PNIPAm nanofiber hydrogels reach swelling equilibrium is 25.8g/g.
PU-g-PNIPAm nanofiber hydrogels go water rate to reach 57.8% in 1min.
Feature that PU-g-PNIPAm nanofiber hydrogels are nonmagnetic.
Comparative example 2
Difference from Example 1 is, in comparative example 1, modified SiO in step 2)2Additional amount be 0, obtain PU-g-
PNIPAm/Fe3O4Composite nano fiber hydrogel, fibre diameter is 410 ± 201nm in hydrogel.Porosity and specific surface integral
It Wei not 87.5% and 13.6m2/g。PU-g-PNIPAm/Fe3O4Composite nano fiber hydrogel reaches swelling ratio when swelling equilibrium
For 18.3g/g.PU-g-PNIPAm/Fe3O4Composite nano fiber hydrogel goes water rate to reach 40.1% in 1min.PU-g-
PNIPAm/Fe3O4The apparent saturation magnetization of composite nano fiber hydrogel is 0.052emu/g.Compared with comparative example 1, implement
The equilibrium swelling ratio of the hydrogel prepared in example 1 and go water rate respectively from 18.3g/g and 40.1% increase to 23.27g/g and
55.8%.It is primarily due to modified SiO2Addition form discrete network pore structure, porosity improves, temperature-responsive rate
It greatly improves.
Comparative example 3
Difference from Example 1 is, in comparative example 3, quenches quenching mixed liquor in 10 DEG C of refrigerators in step 1)
2h finally obtains PU-g-PNIPAm/Fe3O4Composite membrane hydrogel.PU-g-PNIPAm/Fe3O4The porosity of composite membrane hydrogel
It is respectively 60.1% and 6.17g/g with specific surface area.PU-g-PNIPAm/Fe3O4Composite membrane hydrogel equilibrium swelling ratio is
The water rate of going of 10.5g/g, 1min are 10.8%, and apparent saturation magnetization is 0.054emu/g.It is primarily due to quench at 10 DEG C,
It can not occur mutually to separate to form nanofibrous structures, can be only formed normal film pattern, therefore the hole of finally formed hydrogel
Rate and specific surface area reduce significantly, corresponding equilibrium swelling ratio and water rate are gone also to reduce.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (9)
1. the preparation method of a kind of magnetic, temperature collaboration stimuli responsive hydrogel, which comprises the steps of:
Frerrous chloride and iron chloride are dissolved in distilled water, ammonium hydroxide is added, after reaction, obtains magnetic ferroferric oxide nanometer
Grain；
Polyurethane is dissolved in N, the magnetism is added after dissolving completely in N '-dimethyl formamide/tetrahydrofuran in the mixed solvent
Ferroferric oxide nano granules obtain quenching liquid；
After the quenching liquid is quenched at -40~-10 DEG C, N, N '-dimethyl formamide/tetrahydro furan are removed with distilled water
It mutters mixed solvent, freeze-drying obtains polyurethane/Fe 3 O 4 magnetic composite nano fiber；
By the n-isopropyl acrylamide, N, N '-methylene-bisacrylamide and ammonium persulfate are dissolved in distilled water, and addition changes
Property nano silica, after being uniformly dispersed, be added by benzophenone activation polyurethane/Fe 3 O 4 magnetic composite Nano
Fiber is reacted with ultraviolet light irradiation under nitrogen protection, obtains polyurethane grafted poly-N-isopropyl acrylamide/tetra- oxidations three
Ferromagnetism composite nano fiber hydrogel, i.e., the described magnetic, temperature collaboration stimuli responsive hydrogel.
2. the preparation method of magnetic as described in claim 1, temperature collaboration stimuli responsive hydrogel, which is characterized in that the chlorination
Ferrous and iron chloride molar ratio is 1:2, and the concentration of ammonium hydroxide is 1mol/L, and the cool time is 1~3h.
3. the preparation method of magnetic as described in claim 1, temperature collaboration stimuli responsive hydrogel, which is characterized in that the quenching
In liquid, polyurethane, N, the mass ratio of N '-dimethyl formamide, tetrahydrofuran and magnetic ferroferric oxide nanometer particle are 1:(8
~16): (2~6): (0.05~0.1).
4. the preparation method of magnetic as described in claim 1, temperature collaboration stimuli responsive hydrogel, which is characterized in that the modification
Nano silica the preparation method comprises the following steps:
Vinyltriethoxysilane is dissolved in ethyl alcohol, silica is added, is uniformly dispersed, after being ultrasonically treated 2h, centrifugation
Separation, ethanol washing are dried in vacuo at 50 DEG C, obtain modified manometer silicon dioxide.
5. the preparation method of magnetic as claimed in claim 4, temperature collaboration stimuli responsive hydrogel, which is characterized in that the ethylene
Ethyl triethoxy silicane alkane, ethyl alcohol, silica mass ratio be 1:25:1.
6. the preparation method of magnetic as described in claim 1, temperature collaboration stimuli responsive hydrogel, which is characterized in that the poly- ammonia
Ester/Fe 3 O 4 magnetic composite nano fiber activation method are as follows:
Polyurethane/Fe 3 O 4 magnetic composite nano fiber is soaked in the acetone soln of benzophenone, is taken out after 5min,
Vacuum drying, it is spare.
7. the preparation method of magnetic as claimed in claim 6, temperature collaboration stimuli responsive hydrogel, which is characterized in that the poly- ammonia
Ester/Fe 3 O 4 magnetic composite nano fiber, benzophenone, acetone mass ratio be 1:5:95.
8. the preparation method of magnetic as described in claim 1, temperature collaboration stimuli responsive hydrogel, which is characterized in that the N- is different
Propylacrylamide, N, the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate and improved silica be 100:4:(1~
2): (2~4).
9. the preparation method of magnetic as described in claim 1, temperature collaboration stimuli responsive hydrogel, which is characterized in that the N- is different
Polyurethane/ferroferric oxide magnetic nano composite fibre mass ratio after propylacrylamide and activation is 10:(1~1.5).
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